CN116278215A - 一种防雷击用电磁屏蔽复合材料及其制备方法 - Google Patents
一种防雷击用电磁屏蔽复合材料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种防雷击用电磁屏蔽复合材料及其制备方法。所述防雷击用电磁屏蔽复合材料包括依次交替层叠设置的至少一穿孔碳纳米管膜层、至少一碳纤维层,所述穿孔碳纳米管膜层上设置有多个沿所述穿孔碳纳米管膜层的厚度方向贯通的孔洞结构。本发明通过制备穿孔碳纳米管膜层,并通过使穿孔碳纳米管膜层在碳纤维树脂中插层排列,从而实现厚度方向结构强度、导电性和树脂韧性的同时增强,制得的穿孔碳纳米管膜层的界面结合力强且不影响导电性与屏蔽性能,通过插层方式为抗雷击碳基复合材料带来优异力电性能和抗雷击性能,得到轻质高强、高导电、高屏蔽效能的叠层复合材料,同时对复合材料的力学性能具有良好的增强效果。
Description
技术领域
本发明涉及一种电磁屏蔽复合材料,具体涉及一种防雷击用电磁屏蔽复合材料及其制备方法,属于电磁屏蔽材料科学技术领域。
背景技术
碳纤维增强树脂基叠层复合材料因其高比强度、高比刚度、密度小及易加工等特点,在航空航天、飞机蒙皮上的应用广泛,但与金属基材料相比,树脂基复合材料由增强纤维及聚合物组合而成,其导电性能一般较差,在防雷击、电磁屏蔽等领域比较受限。当飞机遭遇雷击时,雷击电流会在雷击附着点附近区域产生巨大的焦耳热,会在复合材料表面产生3000-30000℃的高温,使复合材料电击损坏甚至烧蚀,同时纯树脂基碳纤维板的屏蔽效能一般在30dB左右,外界磁场容易干扰舱内元器件,因此需要通过界面调控提高复合材料的抗雷击、电磁屏蔽性能。
碳纳米管(CNT)材料作为一种重要的一维碳纳米材料,具有多种优异的性能,特别是其优异的导电性能使其成为抗雷电的原材料的重要候选者之一。目前最常见的防雷击方法是在复合材料表面复合一层导电层。如参考专利CN103552296A提出一种碳纳米管粉体填充金属网络的防雷击导电层。参考专利CN102001448A涉及了一种由衬底和在其表面生长的碳纳米管防雷击表面膜。还有CN110337234A提出的一种导电质复合碳纳米管薄膜的耐湿热电磁屏蔽薄膜。截止到目前,通过将碳纳米管粉体分散以及薄膜复合导电质的方式与碳纤维基体复合,获得碳纳米管树脂基复合材料,这些工作均未考虑复合材料复合后的力学性能,且会导致分层,并影响与树脂的结合,如果导电层下面的树脂蒸发,积聚的压力会造成更大的损坏。同时这些材料制备工艺复杂,通常难以同时具有高强度、高导电及高屏蔽效能等复合性能。
具体的,现有技术中碳纳米管以粉体形式与表面导电层结合主要体现在:碳纳米管导电网络不连续均匀,传递效率低下,电导率不足,与表面导电层复合一般采用金属层基体,但由于金属密度大,所以一般采用编制或多孔压缩方式,但局部双层厚度和非均匀厚度,网格在交叉点处也具有较高的电阻率。
目前多研究的抗雷击屏蔽层方式为金属箔片、金属镀层或金属编织网制备复合材料。金属箔片与树脂的结合较差,与碳纤维树脂基体复合后会产生分层,发生雷击后金属箔片下面的树脂蒸发,积聚压力会造成更大破环。金属镀层与箔片有相似的缺点,提高电导率需通过增加镀层厚度的方式,当厚度达到一定水平时,镀层易开裂,通过插层方式影响与树脂的结合性,产生分成。金属编织网的树脂结合性和抗雷击性能优异,但由于孔洞较大,一定频段内屏蔽效能较差,因此其综合性能依然难以提高。
发明内容
本发明的主要目的在于提供一种防雷击用电磁屏蔽复合材料及其制备方法,以克服现有技术中的不足。
为实现前述发明目的,本发明采用的技术方案包括:
本发明实施例提供了一种防雷击用电磁屏蔽复合材料,其包括依次交替层叠设置的至少一穿孔碳纳米管膜层、至少一碳纤维层,所述穿孔碳纳米管膜层上设置有多个沿所述穿孔碳纳米管膜层的厚度方向贯通的孔洞结构。
进一步地,所述防雷击用电磁屏蔽复合材料是将穿孔碳纳米管膜层插层到至少两层碳纤维层之间形成的。
相应的,本发明实施例还提供了所述防雷击用电磁屏蔽复合材料的制备方法,其包括:
提供碳纳米管膜层,并在所述碳纳米管膜层的厚度方向上穿设复数个贯通的孔洞结构,形成穿孔碳纳米管膜层;
将至少一层所述穿孔碳纳米管膜层插层到至少两层碳纤维层之间,并依次交替层叠设置,最后成型固化,制得所述防雷击用电磁屏蔽复合材料。
与现有技术相比,本发明的有益效果在于:
本发明通过制备穿孔碳纳米管膜层,并通过使穿孔碳纳米管膜层在碳纤维树脂中插层排列,从而实现厚度方向结构强度、导电性和树脂韧性的同时增强,制得的穿孔碳纳米管膜层的界面结合力强且不影响导电性与屏蔽性能,通过插层方式为抗雷击碳基复合材料带来优异力电性能和抗雷击性能,得到轻质高强、高导电、高屏蔽效能的叠层复合材料,同时对复合材料的力学性能具有良好的增强效果。
附图说明
为了更清楚地说明本申请实施例或现有技术中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本申请中记载的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。
图1是本发明一典型实施方案中一种防雷击用电磁屏蔽复合材料的结构示意图;
图2是本发明实施例1中不同穿孔间距的碳纳米管膜的屏蔽性能图;
图3是本发明实施例1、对照例1、对照例2中雷击后材料表面的界面CT测试图像;
图4是本发明实施例1、对照例1、对照例2中碳纳米管/碳纤维复合板的电磁屏蔽效能图;
图5是本发明实施例1中所获穿孔碳纳米管/碳纤维复合板的力学性能图。
具体实施方式
为了更好地解决现有的抗雷击碳纤维屏蔽复合材料导电层与树脂层间性能较弱的问题,提高膜类导电层的导电性能,减轻金属类导电层的密度,以提高导电层的比电导率为主,本案发明人经大量研究,得以提出本发明的技术方案,其主要是提出一种碳纤维复合材料层间性能增强的方法,通过穿孔碳纳米管薄膜制造,并通过穿孔碳纳米管薄膜在碳纤维树脂中的插层排列,从而实现厚度方向结构强度、导电性和树脂韧性的同时增强。
如下将对该技术方案、其实施过程及原理等作进一步的解释说明。以下所述为本发明实施例的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明实施例原理的前提下,还可以做出若干改进,这些改进也视为本发明实施例的保护范围。
请参阅图1所示,本发明实施例的一个方面提供的一种防雷击用电磁屏蔽复合材料包括依次交替层叠设置的至少一穿孔碳纳米管膜层、至少一碳纤维层,所述穿孔碳纳米管膜层上设置有多个沿所述穿孔碳纳米管膜层的厚度方向贯通的孔洞结构。
在一些实施方案中,所述防雷击用电磁屏蔽复合材料在经手雷击后的损伤深度最低可达(不超过)0.6mm,屏蔽性能高达97dB以上,弯曲强度高达900~1000MPa。
在一些实施方案中,所述穿孔碳纳米管膜层上设置的孔洞结构的尺寸应该在1~5mm之间,孔间距为1~10mm。
在一些实施方案中,所述防雷击用电磁屏蔽复合材料是将穿孔碳纳米管膜层插层到至少两层碳纤维层之间形成的,插层层数为1~32层。
在一些实施方案中,插层所用的穿孔碳纳米管膜层的厚度应大于10μm。
进一步地,所述穿孔碳纳米管膜层包括多壁碳纳米管膜,但不限于此。
在一些实施方案中,所述穿孔碳纳米管膜层上设置的孔洞结构的形状包括方形、三角形、圆形、多边形等中的至少任意一种,但不限于此。
在一些实施方案中,所述防雷击用电磁屏蔽复合材料还包括金属层,所述金属层设置于穿孔碳纳米管膜层上,且设置有与穿孔碳纳米管膜层上的孔洞结构相对应的通孔。其中,所述金属层的材质包括铜、银、金等中的至少任意一种,但不限于此。具体的,本发明可以引入其他与碳纳米管膜均具有良好导电性的金属同样可对复合材料抗雷击性能进行改善,或镀覆金属的导电层,如铜、银、金等。例如,可以采用Cu-碳纳米管薄膜作为导电层得到分层碳-碳防雷击复合材料,引入高导电金属铜层。
进一步地,所述金属层的厚度在微米级别,金属层以微米厚度沉积在碳纳米管薄膜上。
在一些实施方案中,所述碳纤维层包括碳纤维织物、碳纤维预浸渍料中的至少任意一种。
进一步地,所述碳纤维织物由商业化的碳纤维编织得到,其编织方式可以包括单向、平纹、斜纹、缎纹等中的任意一种或两种以上的组合,但不限于此。
进一步地,所述碳纤维预浸渍料由碳纤维织物和基体树脂复合得到,所述基体树脂可以包括环氧树脂、苯并噁嗪树脂、双马来酰亚胺树脂、聚酰亚胺树脂等中的任意一种或两种以上的组合,但不限于此。
进一步地,所述碳纤维层的厚度为0.02mm~0.25mm。
本发明实施例的另一个方面还提供了一种制备所述防雷击用电磁屏蔽复合材料的方法,其包括:
提供碳纳米管膜层,并在所述碳纳米管膜层的厚度方向上穿设复数个贯通的孔洞结构,形成穿孔碳纳米管膜层;
将至少一层所述穿孔碳纳米管膜层插层到至少两层碳纤维层之间,并依次交替层叠设置,最后成型固化,制得所述防雷击用电磁屏蔽复合材料。
本发明通过穿孔碳纳米管薄膜制造,并通过穿孔碳纳米管薄膜在碳纤维树脂中的插层排列,从而实现厚度方向结构强度、导电性和树脂韧性的同时增强。
在一些实施方案中,所述制备方法包括:采用激光打孔制备所述穿孔碳纳米管膜层。本发明通过穿孔方式可显著提高树脂浸润性,改善碳纤维间分层现象,提高层间力学性能。
进一步地,本发明采用单层及多层碳纳米管膜作为导电层覆于抗雷击复合材料表面,通过插层方式进一步提高抗雷击性能。
进一步地,所述碳纳米管膜层是通过浮动催化化学气相沉积法制得的。
在一更优选的实施方案中,所述制备方法包括:先在碳纳米管膜层上设置金属层,再采用激光打孔制备所述穿孔碳纳米管膜层。
在一些实施方案中,所述成型固化的工艺可以包括热压罐成型、RTM、模压、真空辅助或真空袋成型等中的至少任意一种方式,但不限于此。具体操作按照基体树脂的成型条件执行。
其中,在一些更为具体的实施方案之中,所述防雷击用电磁屏蔽复合材料的制备方法(亦可称为“防雷击用电磁屏蔽复合材料的穿孔-插层的方法”)具体包括:
将浮动催化化学气相沉积法制备的高导电多壁碳纳米管膜通过激光打孔制备穿孔碳纳米管膜层,将其插层到碳纤维织物或碳纤维预浸渍料层间,然后按复合材料的制备工艺和固化工艺得到最终复合材料。其中穿孔尺寸在1~5mm之间,插层层数为1~32层。
该制备方法制得的成品为包含一层或者多层的被压缩的穿孔碳纳米管复合结构的叠层碳纤维复合材料制品。
采用上述技术方案后,本发明通过对碳纳米管物理改性打孔,得到穿孔连续碳纳米管复合结构,再对连续碳纤维叠层复合材料层间进行改性(碳纳米管改性树脂,提高层间结构),通过碳基材料结构的导电连通性和韧性结构提高了叠层复合材料的导电性、韧性,得到优异抗雷电、轻质高强、高导电、高屏蔽效能的叠层复合材料,使得复合结构具有良好导电性,同时对复合材料的力学性能具有良好的增强效果。
本发明制得的穿孔碳纳米管膜层的界面结合力强且不影响的导电性与屏蔽性能,通过插层方式为防雷击用电磁屏蔽复合材料带来的优异力电性能,主要体现在:1)碳纳米管膜优异的导电性;2)碳纳米管膜层厚度影响树脂的浸润性,穿孔改善了界面结构,但不影响导电性,对复合材料的屏蔽效能有着正向的提高作用;3)穿孔碳纳米管膜层通过插层方式较覆于表面具有更好的抗雷击效果,稳定的碳-碳界面结构同样大幅提升了雷击的载流容量;4)此复合材料还具有优异的屏蔽效能。
下面结合若干优选实施例及附图对本发明的技术方案做进一步详细说明,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动的前提下所获得的所有其他实施例,都属于本发明保护的范围。以下实施例中采用的实施条件可以根据实际需要而做进一步调整,未注明的实施条件通常为常规实验中的条件。
实施例1
通过浮动催化化学气相沉积法获得厚度为12μm的碳纳米管薄膜,采用激光打孔制备穿孔碳纳米管膜层。设定孔洞尺寸为孔洞之间的间隔为1mm,测试不同孔洞间距(1-10mm)的穿孔碳纳米管膜SET、SEA及SER,屏蔽性能结果如图2所示,发现当孔洞间隔为1mm时,碳纳米管膜的电磁屏蔽效能最大。
采用真空袋辅助成型工艺,将穿孔碳纳米管薄膜每4层覆于正交叠加的碳纤维单向预浸料上,烘箱中130℃固化1.5h,得到穿孔碳纳米管/碳纤维复合板,复合板的厚度为4.5mm。通过三点弯测试,证明了插层结构依然具有优异力学性能,结果如图5所示。
本案发明人还对前述实施例所获防雷击用电磁屏蔽复合材料的其他性能也进行了测试,例如,测试穿孔碳纳米管/碳纤维复合板的电磁屏蔽效能(图4)及抗雷击性能(图3)。研究结果表明穿孔碳纳米管/碳纤维复合板电磁屏蔽效能高于纯碳纤维复合板,经过CT检测发现雷击后的损伤深度减小,最小为0.59mm。
当然,参照实施例1的步骤,碳纳米管薄膜的打孔还可以是其他尺寸,在1~5mm之间即可。另外,本案发明人还可以将其他层数的穿孔碳纳米管膜层插层到碳纤维层之间,例如插层层数可以是1~32层。其中,碳纤维单向预浸料可以是碳纤维织物与环氧树脂、苯并噁嗪树脂、双马来酰亚胺树脂、聚酰亚胺树脂等基体树脂复合得到的,且碳纤维单向预浸料还可以替换为由碳纤维编织得到的碳纤维织物。
对照例1
通过浮动催化化学气相沉积法获得厚度为10μm的碳纳米管薄膜,采用真空袋辅助成型工艺,将碳纳米管薄膜每4层覆于正交叠加的碳纤维单向预浸料上,烘箱中130℃固化1.5h得到碳纳米管/碳纤维复合板,复合板厚度为4.5mm。
测试碳纳米管/碳纤维复合板的电磁屏蔽效能(图4)及抗雷击性能(图3)。研究结果表明穿孔碳纳米管/碳纤维复合板电磁屏蔽效能高于碳纳米管/碳纤维复合板,经过CT检测发现雷击后的损伤深为0.79mm。
对照例2
采用真空袋辅助成型工艺,将单层穿孔碳纳米管薄膜覆于正交叠加的碳纤维单向预浸料上,烘箱中130℃固化1.5h得到穿孔碳纳米管/碳纤维复合板,复合板厚度为4.5mm。测试碳纳米管/碳纤维复合板的抗雷击性能(图3)。研究结果表明未插层穿孔碳纳米管/碳纤维复合板雷击后的损伤深为0.95mm,高于插层穿孔碳纳米管/碳纤维复合板。
实施例2
通过浮动催化化学气相沉积法获得厚度为12μm的碳纳米管薄膜,通过物理气相沉积法在穿孔碳纳米管膜上沉积500nm的铜层,制备镀铜碳纳米管膜。采用激光打孔制备穿孔碳纳米管膜层。设定孔洞尺寸为孔洞之间的间隔为1mm。
采用真空袋辅助成型工艺,将穿孔镀铜碳纳米管薄膜每4层覆于正交叠加的碳纤维单向预浸料上,烘箱中130℃固化1.5h,得到穿孔碳纳米管/碳纤维复合板,复合板的厚度为4.5mm。通过屏蔽性能测试,证明金属镀层可提高复合板整体的屏蔽效能,结果如图4所示。
此外,本案发明人还参照前述实施例,以本说明书述及的其它原料、工艺操作、工艺条件进行了试验,并均获得了较为理想的结果。
应当理解,上述实施例仅为说明本发明的技术构思及特点,其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施,并不能以此限制本发明的保护范围。凡根据本发明精神实质所作的等效变化或修饰,都应涵盖在本发明的保护范围之内。
Claims (10)
1.一种防雷击用电磁屏蔽复合材料,其特征在于,包括依次交替层叠设置的至少一穿孔碳纳米管膜层、至少一碳纤维层,所述穿孔碳纳米管膜层上设置有多个沿所述穿孔碳纳米管膜层的厚度方向贯通的孔洞结构。
2.根据权利要求1所述的防雷击用电磁屏蔽复合材料,其特征在于:所述穿孔碳纳米管膜层上设置的孔洞结构的尺寸为1~5mm,孔间距为1~10mm;
和/或,所述防雷击用电磁屏蔽复合材料在经手雷击后的损伤深度不超过0.6mm,屏蔽性能在97dB以上,弯曲强度为900~1000MPa。
3.根据权利要求1所述的防雷击用电磁屏蔽复合材料,其特征在于:所述防雷击用电磁屏蔽复合材料是将穿孔碳纳米管膜层插层到至少两层碳纤维层之间形成的,插层层数为1~32层。
4.根据权利要求1所述的防雷击用电磁屏蔽复合材料,其特征在于:所述穿孔碳纳米管膜层的厚度大于10μm;和/或,所述穿孔碳纳米管膜层包括多壁碳纳米管膜。
5.根据权利要求1所述的防雷击用电磁屏蔽复合材料,其特征在于:所述穿孔碳纳米管膜层上设置的孔洞结构的形状包括方形、三角形、圆形、多边形中的至少任意一种。
6.根据权利要求1所述的防雷击用电磁屏蔽复合材料,其特征在于还包括金属层,所述金属层设置于穿孔碳纳米管膜层上,且设置有与穿孔碳纳米管膜层上的孔洞结构相对应的通孔,优选的,所述金属层的材质包括铜、银、金中的至少任意一种,优选的,所述金属层的厚度在微米级别。
7.根据权利要求1所述的防雷击用电磁屏蔽复合材料,其特征在于:所述碳纤维层包括碳纤维织物、碳纤维预浸渍料中的至少任意一种;优选的,所述碳纤维织物由碳纤维编织得到,编织方式包括单向、平纹、斜纹、缎纹中的任意一种或两种以上的组合;优选的,所述碳纤维预浸渍料由碳纤维织物和基体树脂复合得到,尤其优选的,所述基体树脂包括环氧树脂、苯并噁嗪树脂、双马来酰亚胺树脂、聚酰亚胺树脂中的任意一种或两种以上的组合;
和/或,所述碳纤维层的厚度为0.02mm~0.25mm。
8.如权利要求1-7中任一项所述防雷击用电磁屏蔽复合材料的制备方法,其特征在于,包括:
提供碳纳米管膜层,并在所述碳纳米管膜层的厚度方向上穿设复数个贯通的孔洞结构,形成穿孔碳纳米管膜层;
将至少一层所述穿孔碳纳米管膜层插层到至少两层碳纤维层之间,并依次交替层叠设置,最后成型固化,制得所述防雷击用电磁屏蔽复合材料。
9.根据权利要求8所述的制备方法,其特征在于:所述碳纳米管膜层是通过浮动催化化学气相沉积法制得的;和/或,所述制备方法包括:采用激光打孔制备所述穿孔碳纳米管膜层;优选的,所述制备方法包括:先在碳纳米管膜层上设置金属层,再采用激光打孔制备所述穿孔碳纳米管膜层。
10.根据权利要求8所述的制备方法,其特征在于:所述成型固化的工艺包括热压罐成型、RTM、模压、真空辅助或真空袋成型中的至少任意一种方式。
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